Aerogel compositions with enhanced performance

ABSTRACT

Aerogel materials, aerogel composites and the like may be improved by enhancing their smoke suppression, combustion reduction properties. It is additionally useful to provide aerogel based composites compatible with environments conducive to combustion. Such aerogel materials and methods of manufacturing the same are described.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.11/753,815 filed May 25, 2007; which claims benefit of priority fromU.S. Provisional Patent Applications 60/803,189 filed May 25, 2006 and60/865,324 filed Nov. 10, 2006; all of which are incorporated herein byreference in their entirety.

FIELD OF INVENTION

The present invention relates to aerogels providing enhanced performanceand specifically in the area of smoke, fire or flame suppression andreduced combustibility.

SUMMARY OF THE INVENTION

Embodiments of the present invention describe aerogel materialsproviding enhanced performance and specifically in the area of smoke,fire or flame suppression and reduced combustibility. Such materials maycomprise smoke, fire or flame suppressing fillers. In some embodimentsat least some of the fillers also behave as fire retardants. The fillersmay comprise: phosphates, borates, metal silicates, metallocenes,molybdates, stannates, hydroxides, carbonates, zinc oxides, aluminumoxides, antimony oxides, magnesium-zinc blends, magnesium-zinc-antimonyblends, or a combination thereof.

At least some of the fillers may be in hydrated form. Suitable phosphatefillers comprise cyclic phosphates, alkylphosphates, ammoniumpolyphosphates, arylphosphates, alkylarylphosphates or a combinationthereof. Specific examples of preferred phosphates include triethylphosphate, tributyl phosphate, trihexyl phosphate, tridecyl phosphate,tri(2-ethylhexyl)phosphate, trioctyl phosphate, hexyldioctyl phosphate,and the like. In one embodiment phosphate fillers have the generalformula:

wherein: X═OH, OR′, OC(O)R′ or OC(O)NC₃Si(OEt)₃;

R═H, a saturated or unsaturated straight-chain or branched-chain C₁-C₁₇alkyl, most preferably C₁-C₃; and

R′ is a saturated or unsaturated C₁-C₁₇ alkyl, most preferably C₁-C₃.The aerogel material preferably comprises phosphate fillers at a levelof about 1 to 30 percent all by weight of the final composition.

In another embodiment, the borate fillers comprise Magnesium, Sodium,Calcium, Zinc, Tantalum, Nickel, Titanium, Cerium, Potassium, Beryllium,Lithium, Antimony, Aluminum, Manganese, Copper, Strontium, Iron, ammoniaor a combination thereof. Largest dimension of the borate fillers isless than about 100 μm, less than about 50 μm, less than about 10 μm orless than about 5 μm. The aerogel material preferably comprises lessthan about 50%, less than about 30%, less than about 20%, less thanabout 10% or less than about 5% by weight of borate fillers. In anotherembodiment, the metal silicate fillers comprise Beryllium, Magnesium,Calcium, Strontium, Barium, Radium, Aluminum, Iron, Titanium, Manganese,Potassium, Sodium or a combination thereof. Preferably the largestdimension of the metal silicate fillers is less than about 100 μm, lessthan about 50 μm, less than about 10 μm or less than about 5 μm. Alsopreferably, the aerogel material comprises less than about 50%, lessthan about 30%, less than about 20%, less than about 10% or less thanabout 5% by weight of metal silicate fillers. In another embodiment themetallocene fillers comprise Chromium, Cobalt, Hafnium, Iron, Titanium,Vanadium, Ruthenium, Rhodium, Zirconium, Tungsten, Molybdenum, Osmium,or Nickel. In a further embodiment the metallocene fillers have achemical structure:

wherein m=an integer greater than 2 (i.e. 2,3,4 . . . ); and

R=hydrogen, low molecular weight alkyl groups, aryl, alkylaryl, phenyl,methyl, phenyl, or alkylphenyl. Preferably the largest dimension of themetallocene fillers is less than about 100 μm, less than about 50 μm,less than about 10 μm or less than about 5 μm. Also preferably, aerogelmaterial comprises less than about 50%, less than about 30%, less thanabout 20%, less than about 10% or less than about 5% by weight ofmetallocene fillers. In yet another embodiment, the molybdate fillerscomprise: MoS₂, MoO₃, CaMoO₄, Mo₂ O₅, MoS₃, Mo₂S₃, Mo₂O₃, MoO₂, MoS₄,MoCl₃, MoBr₃, PbMoO₄, ammonium 5-molybdocobaltate (III),9-molybdonickelate (IV), 6-molybdoaluminate (III), 6-molybdochromate(III), ammonium dimolybdate, ammonium molybdate, ammoniumheptamolybdate, ammonium octamolybdate, ammonium phosphomolybdates,alkali metal molybdates, alkaline earth molybdates or a combinationthereof. Preferably, the largest dimension of the molybdate fillers isless than about 100 μm, less than about 50 μm, less than about 10 μm orless than about 5 μm. Also preferably, the aerogel material comprisesless than about 50%, less than about 30%, less than about 20%, less thanabout 10% or less than about 5% by weight of molybdate fillers. In someembodiments, the aerogel material itself is based on Silica, Alumina,Titania, Zirconia, Yttria, Hafnia or a combination thereof and mayfurther comprise a fibrous structure. Said fibrous structure maycomprise organic polymer-based fibers, inorganic fibers or a combinationthereof and in forms of a woven, non-woven, mat, felt, batting(e.g.lofty batting), chopped fibers or a combination thereof form. Acorresponding method of preparing aerogel materials with smokesuppressing fillers comprises the steps of:

-   -   (a) forming a gel from a mixture comprising gel precursors and        smoke suppressing fillers; and    -   (b) drying the gel.

Accordingly, said smoke suppressing fillers comprise: phosphates,borates, metal silicates, metallocenes, molybdates, stannates,hydroxides, carbonates, zinc oxides, aluminum oxides, antimony oxides,magnesium-zinc blends, magnesium-zinc-antimony blends, or a combinationthereof. At least some of the smoke suppressing fillers may be inhydrated form. Step (a) may also include dispensing an amount of smokesuppressing fillers into a gel precursor solution, thereby forming amixture, mixing an amount of a smoke suppressing filler with an amountof gel precursor in a suitable solvent; dispensing a mixture comprisingthe fillers and gel precursors, into a fibrous structure or acombination thereof. Alternatively the step of introducing a fibrousstructure into the mixture comprising the fillers and gel precursors maybe carried out. As before, the fibrous structure comprises organicpolymer-based fibers, inorganic fibers or a combination thereof and informs of a mat, felt, batting (e.g. lofty batting) or a combinationthereof. Said gel precursors may comprise Silica, Titania, Zirconia,Alumina, Hafnia, Yttria, Ceria, or a combination thereof. Drying ispreferably carrier out via a supercritical fluid such as but not limitedto supercritical CO₂. As before largest dimension of the fillers used inthe steps above is less than about 100 μm, less than about 50 μm, lessthan about 10 μm or less than about 5 μm. Also, the filler content ofthe dried gel is preferably less than about 50%, less than about 30%,less than about 20%, less than about 10% or less than about 5% byweight. Corresponding aerogel materials and articles of manufacturecomprising the same are low smoke emitting and optionally fireresistant.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 presents an apparatus for measuring the Smoke Density Index (SDI)for aerogels and aerogel composites of the present invention.

DESCRIPTION

Since their discovery, aerogels have been regarded as one of the bestthermal insulating materials ever known. Development of thermal or firebarrier articles based on aerogels continues to be an area of highinterest, but with major challenges. First, the fragile structure of anaerogel (low density and high porosity) poses several difficulties inconforming to irregular surfaces or maintaining integrity in dynamicconditions. Second, when enduring a high heat flux or fire, combustionby-products such as smoke may be generated from an aerogel. This isparticularly undesirable when said articles are placed in enclosed areasproximal to human occupants. Flexible, fiber-reinforced aerogels such asthat commercially available from Aspen Aerogels Inc. (Northborough,Mass.) represent an effective solution for providing conformableaerogels. Still an unmet need exists for mitigation of smoke and othercombustion by-products from aerogels. Yet another unmet need is anaerogel product which is hydrophobic and still substantiallynon-combustible under combustible conditions such as high temperaturesor oxygen rich environments.

Embodiments of the present invention describe aerogels with reducedsmoke emission, reduced combustion, increased compatibility withcombustible environments. Smoke may arise from various components, oradditives in an aerogel when exposed to high thermal events such asfire. In most cases hydrocarbon-based compounds from a component of theaerogel network, from surface modification/functionalization adducts, orfrom un-bonded organic additives or impurities can be responsible forgeneration of smoke or combustion. In one aspect, the present inventioninvolves aerogel materials comprising smoke suppressing fillers. Assuch, the smoke suppressing fillers described herein are distinct fromthe aerogel matrix in which they are embedded. In a further aspect,smoke suppressing fillers are dispersed in a gel precursor solutionwhere upon polymerization (gel formation) and drying the former isincorporated within an aerogel. In an even further aspect the fillersprovide added functionality in the way of smoke suppression.

Within the context of embodiments of the present invention “aerogels” or“aerogel materials” along with their respective singular forms, refer togels containing air as a dispersion medium in a broad sense, and gelsdried with supercritical fluids in a narrow sense. The chemicalcomposition of aerogels can be inorganic, organic (including polymers)or hybrid organic-inorganic. Inorganic aerogels may be based on Silica,Titania, Zirconia, Alumina, Hafnia, Yttria, Ceria, Carbides andNitrides. Organic aerogels can be based on compounds including but arenot limited to: urethanes, resorcinol formaldehydes, polyimide,polyacrylates, chitosan, polymethylmethacrylate, members of the acrylatefamily of oligomers, trialkoxysilyl terminated polydimethylsiloxane,polyoxyalkylene, polyurethane, polybutadiane, melamine-formaldehyde,phenol-furfural, a member of the polyether family of materials orcombinations thereof. Examples of organic-inorganic hybrid aerogelsinclude, but are not limited to: silica-PMMA, silica-chitosan,silica-polyether or possibly a combination of the aforementioned organicand inorganic compounds. Published US patent applications 2005/0192367and 2005/0192366 teach extensively of such hybrid organic-inorganicmaterials and are hereby incorporated by reference in their entirety.

In embodiments of the present invention, smoke suppressing fillers(herein referred to as “fillers”) comprise: phosphates, borates, metalsilicates, metallocenes, molybdates, stannates, hydroxides, carbonates,zinc oxides, aluminum oxides, antimony oxides, magnesium-zinc blends,magnesium-zinc-antimony blends, or a combination thereof. At least someof the preceding fillers may be used in a hydrated form. In oneembodiment, at least one of the fillers functions both as a smokesuppressant and flame retardant.

Phosphate fillers of the present invention include but are not limitedto cyclic phosphates, alkylphosphates, ammonium polyphosphates,arylphosphates and alkarylphosphates. The alkyl phosphates useful forsmoke suppressing fillers may contain from 2 to about 16 carbon atoms inthe alkyl moieties, and more desirably from about 2 to 6. Examples ofsuch alkyl phosphates include triethyl phosphate, tributyl phosphate,trihexyl phosphate, tridecyl phosphate, tri(2-ethylhexyl) phosphate,trioctyl phosphate, hexyldioctyl phosphate, and the like.

Preferred bicyclic phosphates in accordance with this invention arecompounds of formula 1 where:

X═OH, OR′, OC(O)R′ or OC(O)NC₃Si(OEt)₃;

R═H, a saturated or unsaturated straight-chain or branched-chain C₁-C₁₇alkyl, most preferably

C₁-C₃; and

R′ is a saturated or unsaturated C₁-C₁₇ alkyl, most preferably C₁-C₃.

Exemplary preferred bicyclic compounds are2,6,7-trioxa-phosphobicyclo[2.2.2]-octane-4-methanol-l-oxide, and2,6,7-trioxa-l-phosphobicyclo[2.2.2]-octane-4-methanol, acetate,1-oxide. The most preferred bicyclic phosphates comprise an alkoxysilylmoiety (e.g. triethoxysilyl), particularly where the intended gelproduct is silica-based. Known methods in the art may be used to graftsuch moieties onto bicyclic phosphate compounds. One non-limiting routeincludes reaction of a hydroxyl group on the bicyclic phosphate with anisocyanatoalkylalkoxysilane compound (e.g.isocyanatopropyltriethoxysilane). The bicyclic phosphate may be employedat substantially any level to assist in smoke suppression. Desirably,bicyclic phosphates are present at a level of about 1 to 30 percent,preferably about 5 to 25 percent, and most preferably about 10 to 20percent, all by weight of the final composition. U.S. Pat. No. 5,346,938also describes similar uses for bicyclophosphates and is herebyincorporated by reference.

In another embodiment the fillers comprise a borate. The class ofBorates (including metal Borates) comprises a whole host of compoundswith smoke suppressing properties. Exemplary borates may compriseMagnesium, Sodium, Calcium, Zinc, Tantalum, Nickel, Titanium, Cerium,Potassium, Beryllium, Lithium, Antimony, Aluminum, Manganese, Copper,Strontium Iron and ammonia. Examples of borate minerals includeAdmontite (Hydrated Magnesium Borate), Aksaite (Hydrated MagnesiumBorate Hydroxide), Ameghinite (Sodium Borate Hydroxide), Ammonioborite(Hydrated Ammonia Borate), Aristarainite (Hydrated Sodium MagnesiumBorate), Bandylite (Copper Hydroborate Chloride), Behierite (TantalumNiobium Borate), Berborite (Hydrated Beryllium Borate HydroxideFluoride), Biringuccite (Hydrated Sodium Borate Hydroxide), Blatterite(Manganese Magnesium Antimony Iron Borate Oxide), Boracite (MagnesiumBorate Chloride), Borax (Hydrated Sodium Borate), Braitschite (HydratedCalcium Sodium Cerium Lanthanum Borate), Calciborite (Calcium Borate),Chambersite (Manganese Borate Chloride), Chelkarite (Hydrated CalciumMagnesium Borate Chloride), Clinokurchatovite (Calcium Magnesium IronManganese Borate), Colemanite (Hydrated Calcium Borate Hydroxide),Congolite (Iron Magnesium Manganese Borate Chloride), Diomignite(Lithium Borate), Ekaterinite (Hydrated Calcium Borate ChlorideHydroxide), Ericaite (Iron Magnesium Manganese Borate Chloride),Ezcurrite (Hydrated Sodium Borate), Fabianite (Calcium BorateHydroxide), Federovskite (Calcium Magnesium Manganese Borate Hydroxide),Fluoborite (Magnesium Borate Fluoride Hydroxide), Frolovite (CalciumHydroborate), Ginorite (Hydrated Calcium Borate), Gowerite (HydratedCalcium Borate), Halurgite (Hydrated Magnesium Borate Hydroxide),Hambergite (Beryllium Borate Hydroxide), Henmilite (Calcium CopperHydroborate Hydroxide), Hexahydroborite (Hydrated Calcium Hydroborate),Hilgardite (Hydrated Calcium Borate Chloride), Howlite (Calcium BorateSilicate Hydroxide), Hulsite (Iron Magnesium Antimony Borate),Hungchaoite (Hydrated Magnesium Borate Hydroxide), Hydroboracite(Hydrated Calcium Magnesium Borate Hydroxide), Hydrochlorborite(Hydrated Calcium Borate Chloride Hydroxide), Inderborite (HydratedCalcium Magnesium Borate Hydroxide), Inderite (Hydrated Magnesium BorateHydroxide), Inyoite (Hydrated Calcium Borate Hydroxide), Jeremejevite(Aluminum Borate Fluoride Hydroxide), Jimboite (Manganese Borate),Johachidolite (Calcium Aluminum Borate), Kaliborite (Hydrated PotassiumMagnesium Borate Hydroxide), Karlite (Magnesium Aluminum BorateHydroxide Chloride), Kernite (Hydrated Sodium Borate), Korzhinskite(Hydrated Calcium Borate), Kotoite (Magnesium Borate), Kurchatovite(Calcium Magnesium Manganese Iron Borate), Kurnakovite (HydratedMagnesium Borate Hydroxide), Larderellite (Ammonia Borate Hydroxide),Ludwigite Group (Magnesium Iron Nickel Titanium Antimony AluminumBorate), Magnesiohulsite (Magnesium Iron Antimony Borate), Mcallisterite(Hydrated Magnesium Borate Hydroxide), Meyerhofferite (Hydrated CalciumBorate Hydroxide), Nasinite (Hydrated Sodium Borate Hydroxide),Nifontovite (Hydrated Calcium Borate Hydroxide), Nobleite (HydratedCalcium Borate Hydroxide), Nordenskioldine (Calcium Antimony Borate),Olshanskyite (Calcium Hydroborate), Orthopinakiolite (MagnesiumManganese Borate), Penobsquisite (Hydrated Calcium Iron Borate HydroxideChloride), Pentahydroborite (Hydrated Calcium Hydroborate), Peprossiite(Cerium Lanthanum Aluminum Borate), Pinakiolite (Magnesium ManganeseAntimony Borate), Pinnoite (Hydrated Magnesium Borate), Preobrazhenskite(Magnesium Borate Hydroxide), Priceite (Calcium Borate Hydroxide),Pringleite (Hydrated Calcium Borate Hydroxide Chloride), Probertite(Hydrated Sodium Calcium Borate Hydroxide), Rhodizite (Potassium CesiumBeryllium Aluminum Borate), Rivadavite (Hydrated Sodium MagnesiumBorate), Roweite (Calcium Manganese Borate Hydroxide), Ruitenbergite(Hydrated Calcium Borate Hydroxide Chloride), Santite (HydratedPotassium Borate Hydroxide), Sassolite (Boric Acid), Satimolite(Hydrated Potassium Sodium Aluminum Chloride), Sborgite (Hydrated SodiumBorate Hydroxide), Shabynite (Hydrated Magnesium Borate ChlorideHydroxide), Sibirskite (Calcium Borate Hydroxide), Sinhalite (MagnesiumAluminum Borate), Solongoite (Calcium Borate Hydroxide Chloride),Strontioborite (Strontium Borate Hydroxide), Strontioginorite (HydratedStrontium Calcium Borate), Studenitsite (Hydrated Sodium Calcium BorateHydroxide), Suanite (Magnesium Borate), Sussexite (Magnesium BorateHydroxide), Szaibelyite (Magnesium Borate Hydroxide), Takedaite (CalciumBorate), Takeuchiite (Magnesium Manganese Iron Borate), Teepleite(Sodium Hydroborate Chloride), Tertschite (Hydrated Calcium Borate),Tincalconite (Hydrated Sodium Borate), Trembathite (Magnesium IronBorate Chloride), Tunellite (Hydrated Strontium Borate Hydroxide),Tusionite (Manganese Antimony Borate), Tuzlaite (Hydrated Sodium CalciumBorate Hydroxide), Tyretskite (Hydrated Calcium Borate Hydroxide),Ulexite (Hydrated Sodium Calcium Borate), Uralborite (Calcium BorateHydroxide), Veatchite (Hydrated Strontium Borate Hydroxide), Vimsite(Calcium Borate Hydroxide), Volkovskite (Hydrated Potassium CalciumBorate Hydroborate Chloride), Wardsmithite (Hydrated Calcium MagnesiumBorate), Warwickite (Magnesium Titanium Iron Aluminum Borate Oxide),Wightmanite (Hydrated Magnesium Borate Oxide Hydroxide) and Yuanfulite(Magnesium Iron Aluminum Titanium Borate Oxide).

A general formula representing such Borates is: (A)_(w)(J)_(x)(Z)_(y)BO₃

Where A=Ammonia, Water, Hydrogen or a combination thereof

J=at least one of Magnesium, Sodium, Calcium, Tantalum, Cerium,Potassium,

Beryllium, Lithium, Antimony, Aluminum or Strontium

Z=at least one of Manganese, Iron, Copper, Nickel, Titanium and Zinc

Where y+x is greater than or equal to 1 (i.e. x=0,1, 2, . . . ; y=0,1,2, . . . ) and

w is greater than or equal to zero (i.e. w=0,1,2, . . . )

Borate filler compounds of the present invention preferably comprise atleast one transition metal. The most preferred borates for use in thepresent invention are Zinc Borates and variations thereof. Oneparticularly preferred form is hydrated Zinc Borates. The known hydratedzinc borates include ZnOB₂O₃.H₂ O, 2ZnO.3B₂O₃.5H₂O, 2ZnO.3B₂O₃.7H₂O,3ZnO.5B₂O₃.14H₂O (sometimes designated 2ZnO.3B₂O₃.9H₂ O), ZnO.B₂O₃.2H₂O, ZnO.5B₂O₃.5H₂O, 2ZnO.3B₂O₃.3H₂O, and 6ZnO.5B₂O₃.3H₂O. U.S. PatNos. 3,649,172; 4,246,246 and 5,472,644 also teach of Zinc Borates andhydrated forms thereof, all of which are hereby incorporated byreference. The borate fillers are incorporated in the aerogel at levelsof from about 1 to 40 percent by weight of the final aerogel composite.Preferably, betweenabout 2 to 20 percent is used.

The Borate fillers suitable for use are preferably such that theirlargest dimensions are less than about 100 μm, less than about 50 μm,less than about 10 μm or less than about 5 μm. If substantiallyspherical, the “largest dimension” of a filler particle refers to itsdiameter whereas if rod or cone-shaped, a particles length isreferenced. Alternatively, dimensions of the borate fillers are suchthat the fillers readily disperse in a sol solution and do not preventgel formation therein. Preferably, the aerogels (or aerogel composites)of the present invention comprise less than about 50%, less than about30%, less than about 20%, less than about 10% or less than about 5% byweight of Borate fillers.

In another embodiment, metal silicate fillers are used which comprise atleast one alkali earth metal such as Beryllium, Magnesium, Calcium,Strontium, Barium and Radium. Preferably, the filler comprises Calcium.Furthermore the fillers may also comprise other non-alkali earth metalssuch as Aluminum, Iron, Titanium, Manganese, Potassium and Sodium inaddition to the alkali earth metals. It is to be noted that somewater-based gel preparation techniques, such as the water glass process,utilize metal (e.g. sodium) silicates, but only as a silica source. Thisleads to a final dried gel which is essentially free of metal silicatesper se.

A general formula for representing suitable metal silicates is:(Q)_(x)(M)_(y)SiO₃

Where M=an alkali earth metal (Beryllium, Magnesium, Calcium, Strontium,Barium and Radium)

-   -   Q=a non-alkali earth metal (Aluminum, Iron, Titanium, Manganese,        Potassium and Sodium)    -   y=the number of different alkali earth metals and is ≧1 (i.e. 1,        2, 3, . . . )    -   x=the number of different non-alkali earth metals, and is ≧0        (i.e. 0, 1, 2, . . . )

In mineral form, the metal silicate fillers may be structurally groupedinto Nesosilicates, Sorosilicates, Inosilicates Cyclosilicates,Phyllosilicates or Tectosilicates. Specific examples of silicateminerals include: Chloritoid (Iron Magnesium Manganese Aluminum SilicateHydroxide), Datolite (Calcium Boro-Silicate Hydroxide), Euclase(Beryllium Aluminum Silicate Hydroxide), Fosterite (Magnesium Silicate),Gadolinite (Yttrium Iron Beryllium Silicate), Andradite (Calcium IronSilicate), Grossular (Calcium Aluminum Silicate), Pyrope (MagnesiumAluminum Silicate), Spessartine (Manganese Aluminum Silicate), Uvarovite(Calcium Chromium Silicate), Howlite (Calcium Boro-Silicate Hydroxide),Humite (Magnesium Iron Silicate Fluoride Hydroxide), Olivine (MagnesiumIron Silicate), Phenakite (Berylium Silicate), Sphene or Titanite(Calcium Titanium Silicate), Staurolite (Iron Magnesium Zinc AluminumSilicate Hydroxide), Topaz (Aluminum Silicate Fluoride Hydroxide),Uranophane (Hydrated Calcium Uranyl Silicate), Bertrandite (BerylliumSilicate Hydroxide), Danburite (Calcium Boro-Silicate), Allanite(Yttrium Cerium Calcium Aluminum Iron Silicate Hydroxide), Clinozoisite(Calcium Aluminum Silicate Hydroxide), Epidote (Calcium Iron AluminumSilicate Hydroxide), Zoisite (Calcium Aluminum Silicate Hydroxide),Ilvaite (Calcium Iron Silicate Hydroxide), Idocrase or Vesuvianite(Calcium Magnesium Aluminum Silicate Hydroxide),Okenite (HydratedCalcium Silicate), Pectolite (Sodium Calcium Silicate Hydroxide),Aegirine (Sodium Iron Silicate), Augite (Calcium Sodium MagnesiumAluminum Iron Titanium Silicate), Diopside (Calcium Magnesium Silicate),Enstatite (Magnesium Silicate), Hedenbergite (Calcium Iron Silicate),Hypersthene (Magnesium Iron Silicate), Rhodonite (Manganese IronMagnesium Calcium Silicate), Serandite (Sodium Manganese CalciumSilicate Hydroxide), Wollastonite (Calcium Silicate), Actinolite(Calcium Magnesium Iron Silicate Hydroxide), Anthophyllite (MagnesiumIron Silicate Hydroxide), Cummingtonite (Iron Magnesium SilicateHydroxide), Edenite (Sodium Calcium Magnesium Iron Aluminum SilicateHydroxide), Hornblende (Calcium Sodium Magnesium Iron Aluminum SilicateHydroxide), Tremolite (Calcium Magnesium Iron Silicate Hydroxide),Babingtonite (Calcium Iron Manganese Silicate Hydroxide), Inesite(Hydrated Calcium Manganese Silicate Hydroxide), Axinite (CalciumMagnesium Iron Manganese Aluminum Borosilicate Hydroxide), Baratovite(Potassium Lithium Calcium Titanium Zirconium Silicate Fluoride),Benitoite (Barium Titanium Silicate), Beryl (Berylium AluminumSilicate), Cordierite (Magnesium Aluminum Silicate), Eudialyte (SodiumCalcium Cesium Iron Manganese Zirconium Silicate Hydroxide Chloride),Milarite (Hydrated Potassium Calcium Aluminum Beryllium Silicate),Osumilite (Potassium Sodium Iron Magnesium Aluminum Silicate), Dravite(Sodium Magnesium Aluminum Boro-Silicate Hydroxide), Uvite (CalciumSodium Iron Magnesium Aluminum Boro-Silicate Hydroxide), Apophyllite(Hydrated Potassium Sodium Calcium Silicate Hydroxide Fluoride),Cavansite (Hydrated Calcium Vanadium Silicate), Chlorite (Iron MagnesiumAluminum Silicate Hydroxide), Clinochlore (Iron Magnesium AluminumSilicate Hydroxide), Talc (Magnesium Silicate Hydroxide), Gyrolite(Hydrated Calcium Silicate hydroxide), Biotite (Potassium Iron MagnesiumAluminum Silicate Hydroxide Fluoride), Phlogopite (Potassium MagnesiumAluminum Silicate Hydroxide Fluoride), Prehnite (Calcium AluminumSilicate Hydroxide), Serpentine (Iron Magnesium Silicate Hydroxide),Albite (Sodium Aluminum Silicate), Andesine (Sodium Calcium AluminumSilicate), Anorthite (Calcium Aluminum Silicate), Bytownite (CalciumSodium Aluminum Silicate), Labradorite (Sodium Calcium AluminumSilicate), Oligoclase (Sodium Calcium Silicate), Cancrinite (SodiumCalcium Aluminum Silicate Carbonate), Lazurite (Sodium Calcium AluminumSilicate Sulfate Sulfide Chloride), The Quartz Group: (All SiliconDioxide), Scapolite (Calcium Sodium Aluminum Silicate Chloride CarbonateSulfate), Chabazite (Hydrated Calcium Aluminum Silicate), Harmotome(Hydrated Barium Potassium Aluminum Silicate), Heulandite (HydratedSodium Calcium Aluminum Silicate), Laumontite (Hydrated Calcium AluminumSilicate), Mesolite (Hydrated Sodium Calcium Aluminum Silicate),Phillipsite (Hydrated Potassium Sodium Calcium Aluminum Silicate),Scolecite (Hydrated Calcium Aluminum Silicate), Stellerite (HydratedCalcium Aluminum Silicate), Stilbite (Hydrated Sodium Calcium AluminumSilicate) and Thomsonite (Hydrated Sodium Calcium Aluminum Silicate).The most preferred silicate is Wollastonite and its derivatives. U.S.Pat. No. 6,433,049 further discusses Wollastonite and is herebyincorporated by reference.

Inosilicates, especially when comprising calcium, are particularlypreferred although other metal silicates discussed herein are viablealternatives. Examples of single chain calcium-containing Inosilicatesinclude: Okenite (Hydrated Calcium Silicate), Pectolite (Sodium CalciumSilicate Hydroxide), Augite (Calcium Sodium Magnesium Aluminum IronTitanium Silicate), Diopside (Calcium Magnesium Silicate), Hedenbergite(Calcium Iron Silicate), Rhodonite (Manganese Iron Magnesium CalciumSilicate), Serandite (Sodium Manganese Calcium Silicate Hydroxide) andWollastonite (Calcium Silicate.)

The metal silicate fillers suitable for use are preferably such thattheir largest dimensions are less than about 100 μm, less than about 50μm, less than about 10 μm or less than about 5 μm. If substantiallyspherical, the “largest dimension” of a filler particle refers to itsdiameter whereas if rod or cone-shaped, a particles length isreferenced. Alternatively, dimensions of the silicate fillers are suchthat the fillers readily disperse in a sol solution and do not preventgel formation therein. Preferably, the aerogels (or aerogel composites)of the present invention comprise less than about 50%, less than about30%, less than about 20%, less than about 10% or less than about 5% byweight of metal silicate fillers.

In another embodiment the fillers comprise at least one metallocene.Metallocenes are formed by the combination of ionic cyclopentadiene, areactive but aromatic organic anion, with transition metals or metalhalides. A general structure for metallocenes is represented by formula2 where M comprises a metal such as, but limited to: Chromium, Cobalt,Hathium, Iron, Titanium, Vanadium, Ruthenium, Rhodium, Zirconium,Tungsten, Molybdenum, Osmium, or Nickel. These compounds are usuallystable at high temperatures and can contribute to smoke suppressionand/or flame retardation.

Ferrocenes (M=Iron) are the preferred metallocenes for use inembodiments of the present invention. Typically ferrocenes havingmolecular weights greater than about 200 may be used. Other suitableferrocene derivatives, are those having a molecular weight of at least360 and include both simple high molecular weight ferrocene derivativessuch as, but not limited to, monoalkyl and dialkyl substitutedferrocenes, for example, butyldecyl ferrocene, hexadecyl ferrocene,bis-(heptylcyclopentadienyl)-iron, monoalkanoyl and dialkanoylsubstituted ferrocenes, for example, lauroyl ferrocene, and also dimersand polymers such as, for example, vinyl ferrocene copolymers with vinylchloride or acrylic acid methyl methacrylate, or butadiene orcyclopentane; ferrocene condensation dimers and polymers with aldehydesand ketones; ferrocene addition products with polyvinyl chloride andpolyvinylidene chloride; and the like. The high molecular weightferrocene derivatives are known compounds and can be prepared accordingto known procedures such as, for example, described in U.S. Pat. Nos.3,238,185; 3,341,495; 3,350,369; 3,437,634; 3,673,232; 3,770,787 or byany appropriate modifications thereof. For example, ferrocene polymershaving the general formula 3 can be used wherein: m is an integergreater than 2 (i.e. 2,3,4, . . . ), and in some cases 50 and above; and

R is hydrogen, low molecular weight alkyl groups, aryl or alkylaryl,(e.g. phenyl, methyl, phenyl, alkylphenyl, etc.) The cyclopentadienylrings of the ferrocenyl group may be substituted by alkyl groups, aryl,aralkyl, alkaryl, or halogen. One or more of such groups may be presentas substituents on one or both of the cyclopentadienyl rings.

The metallocene fillers suitable for use are preferably such that theirlargest dimensions are less than about 100 μm, less than about 50 μm,less than about 10 μm or less than about 5 μm. If substantiallyspherical, the “largest dimension” of a filler particle refers to itsdiameter whereas if rod or cone-shaped, a particles length isreferenced. Alternatively, dimensions of the metallocene fillers aresuch that the fillers readily disperse in a sol solution and do notprevent gel formation therein. Preferably, the aerogels (or aerogelcomposites) of the present invention comprise less than about 50%, lessthan about 30%, less than about 20%, less than about 10% or less thanabout 5% by weight of metallocene fillers.

In one embodiment, the fillers comprise molybdates and derivativesthereof. Molybdates are minerals with a MoO4 ⁴⁻ ion and at least onemetal exemplified by, but no limited to Wulfenite (PbMoO₄). Examples ofsuitable molybdates for use in the present invention include but are notlimited to: MoS₂, MoO₃, CaMoO₄, Mo₂O₅, MoS₃, Mo₂S₃, Mo₂O₃, MoO₂, MoS₄,MoCl₃, MoBr₃, PbMoO₄, ammonium 5-molybdocobaltate (III),9-molybdonickelate (IV), 6-molybdoaluminate (III), 6-molybdochromate(III), ammonium dimolybdate, ammonium molybdate, ammoniumheptamolybdate, ammonium octamolybdate, ammonium phosphomolybdates,alkali metal molybdates, and alkaline earth molybdates.

The molybdate fillers suitable for use are preferably such that theirlargest dimensions are less than about 100 μm, less than about 50 μm,less than about 10 μm or less than about 5 μm. If substantiallyspherical, the “largest dimension” of a filler particle refers to itsdiameter whereas if rod or cone-shaped, a particles length isreferenced. Alternatively, dimensions of the borate fillers are suchthat the fillers readily disperse in a sol solution and do not preventgel formation therein. Preferably, the aerogels (or aerogel composites)of the present invention comprise less than about 50%, less than about30%, less than about 20%, less than about 10% or less than about 5% byweight of molybdate fillers. U.S. Pat. Nos. 4,680,334 and 4,762,700further describe molybdates and are hereby incorporated by reference.

In another embodiment the fillers comprise antimony. The antimonyconstituent of the flame retardant and/or smoke suppressing compositioncan be any suitable antimony compound dispersible in finely divided formin the solution comprising gel precursors. Exemplary antimony compoundsare antimony trioxide, antimony tetraoxide, antimony pentaoxide,antimony silico-oxide, and other inorganic compounds of antimony, suchas antimony sulfides including antimony tribromide, antimonytetrachloride, antimony trioxide, and the like. U.S. Pat. No. 4,859,365also describes such compounds and the corresponding use.

In another embodiment, the fillers comprise a metal oxide such as butnot limited to zinc oxide, aluminum oxide, antimony oxide, hydrates andderivatives thereof. The iron oxides which can be used Fe₂O₃, Fe₃O₄,FeO, yellow iron oxide, red iron oxide, derivatives and hydratesthereof. These oxides when used should be finely divided so as to insuresubstantially uniform dispersal of the same throughout the gel precursorsolution. Hydrated alumina is a composition generally indicated by theformula Al₂O₃:3H₂O or Al(OH)₃. Thus, on a weight basis hydrated aluminacontains about 65 percent aluminum oxide and about 35 percent water.Commercially available grades of hydrated alumina can be employed in thepractice of the present invention, such as hydrated alumina C-230 soldby Alcoa Chemical Division of Aluminum Company of America. In stillfurther embodiments, magnesium-zinc blends such asmagnesium-zinc-antimony are used. Example of a suitable Antimony Oxideis commercially available under Montana Brand “Low Tint” Antimony Oxideproduced by United States Antimony Corporation. This product is amixture of senarmontite, and typically more than 3% valentinite with anaverage particle size of 1.8 to 3.0 microns.

In embodiments of the present invention, any of the aforementionedfillers may be used in hydrated form (i.e. comprising at least one watermolecule.) Hydrates are useful for flame retarding as well as smokesuppression. U.S. Pat. No. 5,378,753 hereby incorporate by referencedescribes aluminum oxide hydrates Al₂O_(3:x) H₂O (where x=1, 2, 3, . . .). In a similar fashion other metal oxide hydrates can be employed.

In another embodiment the metal oxide fillers are incorporated into theaerogel material further comprise halogenated compounds such aschlorides and bromides. Suitably, 2 parts halogenated compound to metaloxides are used, more preferably three to four parts. For example,antimony oxide may be combined in a 1:4 stoicheometric ratio withantimony tri chloride for added fire retarding capability.

In an embodiment, the fillers are coated or chemically treated forenhanced miscibility, smoke suppression, fire retardation, antioxidationor general stability. This surface modification can allow for betterdispersion in the precursor solution, better compatibility with thesol-gel process in addition to other benefits.

In the preferred embodiments of the present invention, silica aerogelsare discussed whereas the invention as a whole may be practiced withother aerogel compositions as well. The following examples utilize thesol-gel process for preparing gel materials wherein drying of wet-gelsderived from this process yields aerogels. The sol-gel process isdescribed in detail in Brinker C. J., and Scherer G. W., Sol-GelScience; New York: Academic Press, 1990; hereby incorporated byreference. Fillers as used in the examples below may be chosen from anyone, or a combination of the aforementioned fillers.

One mode of practicing embodiments of the present invention comprisesthe steps of:

(a) Forming a gel from a mixture comprising gel precursors and fillers;and

(b) drying the gel.

Another mode of practice comprises the steps of:

(c) dispensing an amount of fillers into a gel precursor solution,thereby forming a mixture;

(d) forming a gel from said mixture; and

(e) drying the gel.

Yet another mode of practice comprises the steps of:

(a) mixing an amount of a filler with an amount of gel precursor in asuitable solvent;

(b) forming a gel from the mixture; and

(c) drying the gel.

In general, the gel precursors of step (a) comprise metal oxides thatare compatible with the sol-gel process where upon polymerization form agel network(s). The silica precursors used may be chosen from but arenot limited to: alkoxysilanes, partially hydrolyzed alkoxysilanes,tetraethoxylsilane (TEOS), partially hydrolyzed TEOS, condensed polymersof TEOS , tetramethoxylsilane (TMOS), partially hydrolyzed TMOS,condensed polymers of TMOS, tetra-n-propoxysilane, partially hydrolyzedand/or condensed polymers of tetra-n-propoxysilane, or combinationsthereof. TEOS, partially hydrolyzed polyethysilicates, andpolyethylsilicates are some of the more common commercially availablesilica precursors. The fillers may be dispensed in the gel precursorsolution at any point before a gel is formed. Gel formation may beviewed as the point where a solution (or mixture) exhibits resistance toflow and/or forms a continuous polymeric network throughout its volume.Preferably the mixture comprising fillers and precursors is a homogenoussolution, conducive to gel formation.

Suitable solvents for use herein include: lower alcohols with 1 to 6carbon atoms, preferably 2 to 4, although other solvents can be used asis known in the art. Ethanol, is typically most favored. Examples ofother useful solvents include but are not limited to: ethyl acetate,ethyl acetoacetate, acetone, dichloromethane, tetrahydrofuran and thelike. Of course in order to achieve a desired level of dispersion orsolution certain gel precursor/filler systems, a multi-solvent approachmay be required.

Generally, gels may be formed via maintaining the mixture in a quiescentstate for a sufficient period of time, changing the pH of the solution,directing a form of energy onto the mixture, or a combination thereof.Exemplary forms of energy include: a controlled flux of electromagnetic(ultraviolet, visible, infrared, microwave), acoustic (ultrasound), orparticle radiation.

Gels may be additionally aged prior to drying to further strengthen thegel structure by increasing the number of cross-linkages. This procedureis useful for preventing potential volume loss during drying, or simplya stronger final gel. Aging can involve: maintaining the gel (prior todrying) at a quiescent state for an extended period, maintaining the gelat elevated temperatures, addition of cross-linkage promoting compoundsor any combination thereof. Aging time period typically requires betweenabout 1 hr and several days. The preferred temperatures are usuallybetween about 10° C. and about 100° C.

Drying plays an important role in engineering the properties ofaerogels, such as porosity and density which influence the materialthermal conductivity. To date, numerous drying methods have beenexplored. U.S. Pat. No. 6,670,402 teaches drying via rapid solventexchange of solvent(s) inside wet gels using supercritical CO₂ byinjecting supercritical, rather than liquid, CO₂ into an extractor thathas been pre-heated and pre-pressurized to substantially supercriticalconditions or above to produce aerogels. U.S. Pat. No. 5,962,539describes a process for obtaining an aerogel from a polymeric materialthat is in the form a sol-gel in an organic solvent, by exchanging theorganic solvent for a fluid having a critical temperature below atemperature of polymer decomposition, and supercritically drying thefluid/sol-gel. U.S. Pat. No. 6,315,971 discloses processes for producinggel compositions comprising: drying a wet gel comprising gel solids anda drying agent to remove the drying agent under drying conditionssufficient to minimize shrinkage of the gel during drying. Also, U.S.Pat. No. 5,420,168 describes a process whereby Resorcinol/Formaldehydeaerogels can be manufactured using a simple air drying procedure.Finally, U.S. Pat. No. 5,565,142 herein incorporated by referencedescribes subcritical drying techniques. The embodiments of the presentinvention can be practiced with drying using any of the abovetechniques. In some embodiments, it is preferred that the drying isperformed at vacuum to below super-critical pressures (pressures belowthe critical pressure of the fluid present in the gel at some point) andoptionally using surface modifying agents.

Fiber-reinforced aerogels as previously described may be prepared withfillers according to the present invention to obtain conformable aerogelcomposites with reduced smoke emission. Optionally, at least some of thefillers also provide flame retardancy. This can be accomplished bydispensing chopped fibers, a fibrous structure or both into a mixture(solution) comprising gel precursors and fillers. Suitable fibrousstructures include, but are not limited to wovens, non-wovens, mats,felts, battings (e.g. lofty batting) and combinations thereof.Alternatively, said mixture may be transferred into a fibrous structure,with or without chopped fibers. Of course in either case, the fibrousstructure may be completely or incompletely submerged in the solutioncomprising the precursors. In all such cases, gel formation followed bydrying results in fiber-reinforced aerogel composites. Aerogelcomposites reinforced with a fibrous batting, herein referred to as“blankets”, are particularly useful for applications requiringflexibility since they are highly conformable and provide excellentthermal conductivity. Aerogel blankets and similar fiber-reinforcedaerogel composites are described in published US patent application2002/0094426A1 and U.S. Pat. Nos. 6,068,882; 5,789,075; 5,306,555;6,887,563 and 6,080,475 all hereby incorporated by reference, in theirentirety.

Accordingly, a mode of preparing fiber-reinforced aerogel compositescomprises the steps of:

(a) dispensing a mixture comprising fillers and gel precursors, into afibrous structure;

(b) forming a gel from said mixture; and

(c) drying the gel.

Another method comprises the steps of:

(a) dispensing an amount of fillers into a gel precursor solution,thereby forming a mixture;

(b) introducing a fibrous structure into said mixture;

(c) forming a gel from said mixture; and

(d) drying the gel.

Another method comprises the steps of:

(a) dispensing an amount of fillers into a gel precursor solution,thereby forming a mixture;

(b) introducing the mixture into a fibrous structure;

(c) forming a gel from said mixture; and

(d) drying the gel.

Yet another method comprises the steps of:

(a) dispensing a gel precursor solution into a fibrous structure;

(b) dispensing an amount of fillers into the gel precursor solution;

(c) forming a gel from said solution; and

(d) drying the gel.

Still, another method comprises the steps of:

(a) dispensing an amount of fillers into a fibrous structure;

(b) introducing a gel precursor solution into said fibrous structure;

(c) forming a gel from said solution; and

(d) drying the gel.

In an embodiment, any of the ingredients, fillers or other materialsdescribed in the present patent application may be used in any part of afinal system. In other words, they may be designed to be outside theaerogel material, as part of the aerogel material, as part of theaerogel composite, as part of the fiber reinforcement or any otherpossibilities thereof.

Alternatively, fibers comprising one or more of the ingredients orfillers may be used. They may be preferred in some instances as one neednot add a specific ingredient separately.

In another embodiment, the fibers are chosen such that the organiccontent of the fibers in minimal. Alternatively, organic content isreduced in the fibers by processes such as pyrolysis where the organiccontent is converted into carbon. Any binders present in the fibers areavoided and reduced in amount to reduce the overall organic content.

In another embodiment, the organic content of the aerogel composite isreduced and preferably considerably reduced. Additionally, variousfillers and ingredients described in the present patent application areused to reduce the combustibility of the resulting composites.

In an embodiment, the composition of the product comprises a magnesiumhydroxide or a derivative or analog thereof, from 0.1wt % to 50wt % ofthe aerogel matrix and preferably from 15wt % to 50wt % of the aerogelmatrix. Without being bound by a specific theory or mechanism, in anembodiment, Magnesium hydroxide, also commonly referred to as magnesiumdihydroxide or MDH, may serve as a flame retardant on a number oflevels. Flame retardants can function to reduce flammability in 5different ways: (1) physical dilution, (2) gas dilution, (3) thermalquenching, (4) formation of protective coatings or barrier layers, (5)chemical interaction. Magnesium hydroxide in one instance reducesflammability via physical dilution by replacing a portion of flammablepolymer fibers, carbon fibers, surface modified silica, or other surfacemodified metal oxides. Magnesium hydroxide in an instant reducesflammability via gas dilution based on its release of water duringthermal decomposition. This water generation helps to exclude oxygen anddilute the concentration of flammable gases during combustion. Magnesiumhydroxide in an instant reduces flammability via thermal quenching dueto its endothermic decomposition that absorbs heat from the system andmay prevent or prolong the onset of ignition and will retard thecombustion of flammable materials. In addition, magnesium hydroxide maycontribute to char formation in organic materials and the formation ofmagnesium oxide upon decomposition may aid in smoke suppression andpromote the formation of a barrier layer that limits flammability.

In an embodiment, the composition of the product comprises an aluminumhydroxide or a derivative or analog thereof, from 0.1wt % to 50wt % ofthe aerogel matrix and preferably from 15wt % to 50wt % of the aerogelmatrix. Aluminum hydroxide, also commonly referred to as aluminatrihydrate or ATH, can serve as a flame retardant on a number of levels.Without being bound by a specific theory or mechanism, in an embodiment,Aluminum hydroxide reduces flammability via physical dilution byreplacing a portion of flammable polymer fibers, carbon fibers, surfacemodified silica, or other surface modified metal oxides. Aluminumhydroxide in another instant reduces flammability via gas dilution basedon its release of water during thermal decomposition. This watergeneration helps to exclude oxygen and dilute the concentration offlammable gases during combustion. Aluminum hydroxide in another instantreduces flammability via thermal quenching due to its endothermicdecomposition that absorbs heat from the system and may prevent orprolong the onset of ignition and will retard the combustion offlammable materials. In addition, aluminum hydroxide may contribute tochar formation in organic materials and the formation of aluminum oxideupon decomposition may aid in smoke suppression and promote theformation of a barrier layer that limits flammability.

In an embodiment, the composition of the product comprises Zinc borateor a derivative or analog thereof, from 0.1wt % to 50wt % of the aerogelmatrix and preferably, from 3wt % to 20wt % of the aerogel matrix. Zincborate, formally dodecaboron tetrazinc docosaoxide heptahydrate andrelated compounds such as diboron tetrazinc heptaoxide hydrate andhexaboron tetrazinc decaaoxide, can serve as a flame retardant on anumber of levels. Without being bound by a specific theory or mechanism,in an embodiment, Zinc borate in an instant reduces flammability viaphysical dilution by replacing a portion of flammable polymer fibers,carbon fibers, surface modified silica, or other surface modified metaloxides. Zinc borate hydroxide in another instant reduces flammabilityvia gas dilution based by releasing water of hydration at elevatedtemperatures. This water generation helps to exclude oxygen and dilutethe concentration of flammable gases during combustion. Zinc borate inyet another instant reduces flammability via formation of protectivecoatings or barrier layers. Zinc borate promotes char formation in avariety of organic systems. It also contributes to the formation ofglassy or ceramic materials to serve as barrier layers and may actsynergistically with ATH and MDH in flame and smoke suppression.

In an embodiment, the composition of the product comprises a calciumsilicate or a derivative or analog thereof, including calcium metasilicate from 0.1 wt % to 50 wt % of the aerogel matrix and preferablyfrom 2 wt % to 10 wt % of the aerogel matrix. Without being bound by aspecific theory or mechanism, in an embodiment, Calcium silicate in aninstant reduces flammability via physical dilution by replacing aportion of flammable polymer fibers, carbon fibers, surface modifiedsilica, or other surface modified metal oxides. Calcium silicate inanother instant reduces flammability via formation of protectivecoatings or barrier layers. Calcium silicate can contribute to charformation and enhance the mechanical properties of char layers in avariety of organic systems. It also contributes to the formation ofglassy or ceramic materials to serve as barrier layers in a variety ofinorganic systems and may act synergistically with inorganic flameretardants (ATH, MDH, etc.), boron compounds (boric acid, zinc borate,etc.), or the silica or other metal oxides of the aerogel matrix orflame or smoke suppressant systems.

In an embodiment, the composition of the product comprises a waterabsorbing or hygroscopic component in various percentages. Without beingbound by a specific theory or mechanism, Such components would behelpful in reducing flammability or combustibility by releasing anybound water. A non-limiting examples of such components includemontmorillonite, illite, bentonite, vermiculite, perlite, saponite andhectorite. Such materials may also be included in other components ofany product such as fibers, which may be desirable in some instances.

In am embodiment, products may comprise zinc borate or a derivative oranalog thereof, in 0-20% wt, silica or a derivative or analog thereof,in 0-75% wt, a calcium silicate or a derivative or analog thereof, in0-15% wt, a magnesium hydroxide or a derivative or analog thereof, in1-40% wt or aluminum hydroxide or a derivative or analog thereof(including alumina trihydrate) in 1-40% wt.

For optimal thermal insulation, aerogels can be further opacified toreduce the radiative component of heat transfer. At any point prior togel formation, opacifying compounds may be dispersed into the mixturecomprising gel precursors. Examples of opacifying compounds include andare not limited to: B₄C, Diatomite, Manganese ferrite, MnO , NiO , SnO,Ag₂O, Bi₂O₃, TiC, WC, carbon black, titanium oxide, iron titanium oxide,zirconium silicate, zirconium oxide, iron (I) oxide, iron (III) oxide,manganese dioxide, iron titanium oxide (ilmenite), chromium oxide,silicon carbide or mixtures thereof.

Aerogels may be surface treated to impart or improve hydrophobicity. Thehydrophobic treatment is carried out by reacting a hydroxy moiety of asilanol group present on a surface of the wet-gel compound (silica gel)with a functional group of a hydrophobing agent thereby converting thesilanol group into a hydrophobic group of the hydrophobicity-imparting(water repelleing) agent. For example, the hydrophobing treatment can becarried out by immersing a gel in a hydrophobicity-imparting solution ofa hydrophobing agent in a solvent, and mixing the gel and the solutionto allow the hydrophobicity-imparting agent to permeate the gel, whileif necessary, heating such a gel mixture so that ahydrophobicity-imparting reaction occurs. Examples of the solvent foruse in the hydrophobic treatment include methanol, ethanol, isopropanol,xylene, toluene, benzene, N,N-dimethylformamide, hexamethyldisiloxaneand the like. There is no particular limit in selection of the solvent,in so far as the solvent can easily dissolve the hydrophobing agent andcan replace the solvent contained in the gel before the hydrophobictreatment. Where the supercritical drying is carried out after thehydrophobic treatment, the solvent to be used in the hydrophobictreatment is preferably a medium that facilitates the supercriticaldrying (e.g., methanol, ethanol, isopropanol, liquefied carbon dioxide,gaseous carbon dioxide or the like), or a medium which can be replacedwith the former medium. Examples of the hydrophobic agent includehexamethyldisilazane, hexamethyldisiloxane, trimethylmethoxysilane,dimethyldimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane,trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane andthe like. Hydrophobic treatments are further described in U.S. Pat. No.5,565,142 hereby incorporated by reference.

However, hydrophobic agents often comprise hydrocarbon components whichyield smoke upon incomplete combustion or contribute to combustion orthe heat of combustion. Likewise aging compounds useful for furtherstrengthening the gel network may yield smoke or contribute tocombustion if not fully removed from the gel structure. Therefore, inthis case it is desirable to minimize the residual hydrocarboncomponents in the aerogel.

The Smoke Density Index (SDI) for aerogels and aerogel composites of thepresent invention may be estimated according to ASTM E84. Based on apreviously tested sample(s) according to ASTM E84, an apparatus such asthat of FIG. 1 can be set up to estimate SDI values for other samples.FIG. 1 represents an apparatus utilized for a pseudo-SDI calculation ofvarious aerogel samples where the samples are placed on top of acrucible furnace 2 and subjected to a high radiant heat flux. The smokegenerated from the samples is collected by a conical duct 4, and guidedto a region penetrated by light from a light source 6 which is measuredby a light meter 8. An external fan 10 assists in moving the smokethrough the system. The smoke density of the samples would be estimatedvia light obstruction technique while exposed to 1000° C. for 15minutes.

The following examples merely serve to assist in understanding certainaspects of the present invention and therefore may not be used to limitthe scope thereof in any manner.

EXAMPLE 1

Firebrake® a commercially available Zinc Borate available from Luzenacis used as filler. Firebrake® fillers are first dispersed in an ethanoland/or water medium. The mixture may be mixed and/or agitated asnecessary to achieve a uniform dispersion of fillers in said medium.Mixing/agitation times typically require about 1 hr, although longertimes may be needed to achieve a uniform dispersion. Said dispersion iscombined with a solution comprising partially hydrolyzedethylpolysilicates (gel precursors) wherein a gel is prepared therefrom.To assist the gel formation (polymerization) reaction, said mixturecomprising the fillers and gel precursors further comprises a catalyst(e.g. ammonia as 5% v:v ammonia in ethanol). A gel is typically formedbetween 4 minutes and 14 hours depending if a gel promoting step (e.g.,catalyst, heat, etc.) is employed. Of course gel times may lie outsideof this range depending on the concentration of species, identity of thespecies (type of filler, precursor, etc.), type of medium, reactionconditions (temperature, pressure, etc.) or others. For preparing thecorresponding fiber-reinforced aerogel composites, the mixture iscombined with a lofty batting or a felt prior to gellation. The fillercontent used is between 1-50% wt relative to the final composite. Thegel precursor concentration and volume of the mixture comprising thesame are chosen based on the desired target density of the final gel.Once the gel is formed, it is treated with HMDZ and subjected to agingunder basic conditions, and kept in a quiescent state. The gel is rinsedto remove water and base. Next the strengthened gel is placed in anautoclave and subjected to drying via supercritical CO₂.

EXAMPLE 2

Ammoniumoctamolybdate commercially available from H.C. Starck is used asfiller. Ammoniumoctamolybdate fillers and are first dispersed in anethanol and/or water medium. The mixture may be mixed and/or agitated asnecessary to achieve a uniform dispersion of fillers in said medium.Mixing/agitation times typically require about 1 hr, although longertimes may be needed to achieve a uniform dispersion. Said dispersion iscombined with a solution comprising partially hydrolyzedethylpolysilicates (gel precursors) wherein a gel is prepared therefrom.To assist the gel formation (polymerization) reaction, said mixturecomprising the fillers and gel precursors further comprises a catalyst(e.g. ammonia as 5% vol ammonia in ethanol). A gel is typically formedbetween 4 minutes and 14 hours depending if a gel promoting step (e.g.,catalyst, heat, etc.) is employed. Of course gel times may lie outsideof this range depending on the concentration of species, identity of thespecies (type of filler, precursor, etc.), type of medium, reactionconditions (temperature, pressure, etc.) or others. For preparing thecorresponding fiber-reinforced aerogel composites, the mixture iscombined with a lofty batting or a felt prior to gellation. The fillercontent used is between 1-50% wt relative to the final composite. Thegel precursor concentration and volume of the mixture comprising thesame are chosen based on the desired target density of the final gel.Once the gel is formed, it is treated with HMDZ and subjected to agingunder basic conditions, and kept in a quiescent state. The gel is rinsedto remove water and base. Next the strengthened gel is placed in anautoclave and subjected to drying via supercritical CO₂.

EXAMPLE 3

Ferrocene or a derivative thereof is obtained from Yixing WeitePetrochemical Additives Plant. The ferrocene fillers and are firstdispersed in an ethanol and/or water medium. The mixture may be mixedand/or agitated as necessary to achieve a uniform dispersion of fillersin said medium. Mixing/agitation times typically require about 1 hr,although longer times may be needed to achieve a uniform dispersion.Said dispersion is combined with a solution comprising partiallyhydrolyzed ethylpolysilicates (gel precursors) wherein a gel is preparedtherefrom. To assist the gel formation (polymerization) reaction, saidmixture comprising the fillers and gel precursors further comprises acatalyst (e.g. ammonia as 5% v:v ammonia in ethanol). A gel is typicallyformed between 4 minutes and 14 hours depending if a gel promoting step(e.g., catalyst, heat, etc.) is employed. Of course gel times may be lieoutside of this range depending on the concentration of species,identity of the species (type of filler, precursor, etc.), type ofmedium, reaction conditions (temperature, pressure, etc.) or others. Forpreparing the corresponding fiber-reinforced aerogel composites, themixture is combined with a lofty batting or a felt prior to gellation.The filler content used is between 1-50% wt relative to the finalcomposite. The gel precursor concentration and volume of the mixturecomprising the same are chosen based on the desired target density ofthe final gel. Once the gel is formed, it is subjected to aging viaHMDZ, and kept in a quiescent state. Next the strengthened gel is placedin an autoclave and subjected to drying via supercritical CO₂.

EXAMPLE 4

NYAD® 5000, a commercially available form of Wollastonite from NYCOMinerals Inc. is used as filler. Nyad® 5000 fillers and are firstdispersed in an ethanol and/or water medium. The mixture may be mixedand/or agitated as necessary to achieve a uniform dispersion of fillersin said medium. Mixing/agitation times typically require about 1 hr,although longer times may be needed to achieve a uniform dispersion.Said dispersion is combined with a solution comprising partiallyhydrolyzed ethylpolysilicates (gel precursors) wherein a gel is preparedtherefrom. To assist the gel formation (polymerization) reaction, saidmixture comprising the fillers and gel precursors further comprises acatalyst (e.g. ammonia as 5% v:v ammonia in ethanol). A gel is typicallyformed between 4 minutes and 14 hours depending if a gel promoting step(e.g., catalyst, heat, etc.) is employed. Of course gel times may lieoutside of this range depending on the concentration of species,identity of the species (type of filler, precursor, etc.), type ofmedium, reaction conditions (temperature, pressure, etc.) or others. Forpreparing the corresponding fiber-reinforced aerogel composites, themixture is combined with a lofty batting or a felt prior to gellation.The filler content used is between 1-50% wt relative to the finalcomposite. The gel precursor concentration and volume of the mixturecomprising the same are chosen based on the desired target density ofthe final gel. Once the gel is formed, it is treated with HMDZ andsubjected to aging under basic conditions, and kept in a quiescentstate. The gel is rinsed to remove water and base. Next the strengthenedgel is placed in an autoclave and subjected to drying via supercriticalCO₂.

EXAMPLE 5

Bicyclophosphates with alkoxysilyl moieties are used as filler. Thesefillers and are first dissolved in an ethanol and/or water medium. Themixture may be mixed and/or agitated as necessary to achieve a uniformsolution of fillers in said medium. Mixing/agitation times typicallyrequire about 1 hr, although longer times may be needed to achieve auniform solution. Said mixture is combined with a solution comprisingpartially hydrolyzed ethylpolysilicates gel precursors) wherein a gel isprepared therefrom. To assist the gel formation (polymerization)reaction, said mixture comprising the fillers and gel precursors furthercomprises a catalyst (e.g.

ammonia as 5% v:v ammonia in ethanol). A gel is typically formed between4 minutes and 14 hours depending if a gel promoting step (e.g.,catalyst, heat, etc.) is employed. Of course gel times may lie outsideof this range depending on the concentration of species, identity of thespecies (type of filler, precursor, etc.), type of medium, reactionconditions (temperature, pressure, etc.) or others. For preparing thecorresponding fiber-reinforced aerogel composites, the mixture iscombined with a lofty batting or a felt prior to gellation. The fillercontent used is between 1-50% wt relative to the final composite. Thegel precursor concentration and volume of the mixture comprising thesame are chosen based on the desired target density of the final gel.Once the gel is formed, it is treated with HMDZ and subjected to agingunder basic conditions, and kept in a quiescent state. The gel is rinsedto remove water and base. Next the strengthened gel is placed in anautoclave and subjected to drying via supercritical CO₂.

EXAMPLE 6

3N® ZS-232, a commercially available form of zinc stannate from 3NInternational, Inc. is used as filler. 3N® ZS-232 fillers and are firstdispersed in an ethanol and/or water medium. The mixture may be mixedand/or agitated as necessary to achieve a uniform dispersion of fillersin said medium. Mixing/agitation times typically require about l hr,although longer times may be needed to achieve a uniform dispersion.Said dispersion is combined with a solution comprising partiallyhydrolyzed ethylpolysilicates (gel precursors) wherein a gel is preparedtherefrom. To assist the gel formation (polymerization) reaction, saidmixture comprising the fillers and gel precursors further comprises acatalyst (e.g. ammonia as 5% v:v ammonia in ethanol). A gel is typicallyformed between 4 minutes and 14 hours depending if a gel promoting step(e.g., catalyst, heat, etc.) is employed. Of course gel times may lieoutside of this range depending on the concentration of species,identity of the species (type of filler, precursor, etc.), type ofmedium, reaction conditions (temperature, pressure, etc.) or others. Forpreparing the corresponding fiber-reinforced aerogel composites, themixture is combined with a lofty batting or a felt prior to gellation.The filler content used is between 1-50% wt relative to the finalcomposite. The gel precursor concentration and volume of the mixturecomprising the same are chosen based on the desired target density ofthe final gel. Once the gel is formed, it is treated with HMDZ andsubjected to aging under basic conditions, and kept in a quiescentstate. The gel is rinsed to remove water and base. Next the strengthenedgel is placed in an autoclave and subjected to drying via supercriticalCO₂.

EXAMPLE 7

LT grade 3N® Brand antimony trioxide, a commercially available form ofAntimony oxide from 3N International, Inc. is used as filler. The LTgrade 3N® Brand antimony trioxide fillers are first dispersed in anethanol and/or water medium. This mixture may be mixed and/or agitatedas necessary to achieve a uniform dispersion of fillers in said medium.Mixing/agitation times typically require about 1 hr, although longertimes may be needed to achieve a uniform dispersion. Said dispersion iscombined with a solution comprising partially hydrolyzedethylpolysilicates (gel precursors) wherein a gel is prepared therefrom.To assist the gel formation (polymerization) reaction, said mixturecomprising the fillers and gel precursors further comprises a catalyst(e.g. ammonia as 5% v:v ammonia in ethanol). A gel is typically formedbetween 4 minutes and 14 hours depending if a gel promoting step (e.g.,catalyst, heat, etc.) is employed. Of course gel times may lie outsideof this range depending on the concentration of species, identity of thespecies (type of filler, precursor, etc.), type of medium, reactionconditions (temperature, pressure, etc.) or others. For preparing thecorresponding fiber-reinforced aerogel composites, the mixture iscombined with a lofty batting or a felt prior to gellation. The fillercontent used is between 1-50% wt relative to the final composite. Thegel precursor concentration and volume of the mixture comprising thesame are chosen based on the desired target density of the final gel.Once the gel is formed, it is treated with HMDZ and subjected to agingunder basic conditions, and kept in a quiescent state. The gel is rinsedto remove water and base. Next the strengthened gel is placed in anautoclave and subjected to drying via supercritical CO₂.

EXAMPLE 8

Hydrated alumina, commercially available from Alcoa, Inc. is used asfiller. Hydrated alumina fillers are first dispersed in an ethanoland/or water medium. This mixture may be mixed and/or agitated asnecessary to achieve a uniform dispersion of fillers in said medium.Mixing/agitation times typically require about 1 hr, although longertimes may be needed to achieve a uniform dispersion. Said dispersion iscombined with a solution comprising partially hydrolyzedethylpolysilicates (gel precursors) wherein a gel is prepared therefrom.To assist the gel formation (polymerization) reaction, said mixturecomprising the fillers and gel precursors further comprises a catalyst(e.g. ammonia as 5% v:v ammonia in ethanol). A gel is typically formedbetween 4 minutes and 14 hours depending if a gel promoting step (e.g.,catalyst, heat, etc.) is employed. Of course gel times may lie outsideof this range depending on the concentration of species, identity of thespecies (type of filler, precursor, etc.), type of medium, reactionconditions (temperature, pressure, etc.) or others. For preparing thecorresponding fiber-reinforced aerogel composites, the mixture iscombined with a lofty batting or a felt prior to gellation. The fillercontent used is between 1-50% wt relative to the final composite. Thegel precursor concentration and volume of the mixture comprising thesame are chosen based on the desired target density of the final gel.Once the gel is formed, it is treated with HMDZ and subjected to agingunder basic conditions, and kept in a quiescent state. The gel is rinsedto remove water and base. Next the strengthened gel is placed in anautoclave and subjected to drying via supercritical CO₂.

EXAMPLE 9

Montana Brand “Low Tint” Antimony Oxide produced by United StatesAntimony Corporation is used as filler. The fillers are first dispersedin an ethanol and/or water medium. This mixture may be mixed and/oragitated as necessary to achieve a uniform dispersion of fillers in saidmedium. Mixing/agitation times typically require about l hr, althoughlonger times may be needed to achieve a uniform dispersion. Saiddispersion is combined with a solution comprising partially hydrolyzedethylpolysilicates (gel precursors) wherein a gel is prepared therefrom.To assist the gel formation (polymerization) reaction, said mixturecomprising the fillers and gel precursors further comprises a catalyst(e.g. ammonia as 5% v:v ammonia in ethanol). A gel is typically formedbetween 4 minutes and 14 hours depending if a gel promoting step (e.g.,catalyst, heat, etc.) is employed. Of course gel times may lie outsideof this range depending on the concentration of species, identity of thespecies (type of filler, precursor, etc.), type of medium, reactionconditions (temperature, pressure, etc.) or others. For preparing thecorresponding fiber-reinforced aerogel composites, the mixture iscombined with a lofty batting or a felt prior to gellation. The fillercontent used is between 1-50% wt relative to the final composite. Thegel precursor concentration and volume of the mixture comprising thesame are chosen based on the desired target density of the final gel.Once the gel is formed, it is treated with HMDZ and subjected to agingunder basic conditions, and kept in a quiescent state. The gel is rinsedto remove water and base. Next the strengthened gel is placed in anautoclave and subjected to drying via supercritical CO₂.

EXAMPLE 10

3N® ZS-232, from 3N International, Inc. and Hydrated alumina, fromAlcoa, Inc are combined in 1:1 stoichiometric ratio as fillers. Thefillers are first dispersed in an ethanol and/or water medium. Thismixture may be mixed and/or agitated as necessary to achieve a uniformdispersion of fillers in said medium. Mixing/agitation times typicallyrequire about 1 hr, although longer times may be needed to achieve auniform dispersion. Said dispersion is combined with a solutioncomprising partially hydrolyzed ethylpolysilicates (gel precursors)wherein a gel is prepared therefrom. To assist the gel formation(polymerization) reaction, said mixture comprising the fillers and gelprecursors further comprises a catalyst (e.g. ammonia as 5% v:v ammoniain ethanol). A gel is typically formed between 4 minutes and 14 hoursdepending if a gel promoting step (e.g., catalyst, heat, etc.) isemployed. Of course gel times may lie outside of this range depending onthe concentration of species, identity of the species (type of filler,precursor, etc.), type of medium, reaction conditions (temperature,pressure, etc.) or others. For preparing the correspondingfiber-reinforced aerogel composites, the mixture is combined with alofty batting or a felt prior to gellation. The filler content used isbetween 1 -50% wt relative to the final composite. The gel precursorconcentration and volume of the mixture comprising the same are chosenbased on the desired target density of the final gel. Once the gel isformed, it is treated with HMDZ and subjected to aging under basicconditions, and kept in a quiescent state. The gel is rinsed to removewater and base. Next the strengthened gel is placed in an autoclave andsubjected to drying via supercritical CO₂.

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference to the sameextent as if each reference were individually and specifically indicatedto be incorporated by reference and were set forth in its entiretyherein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the invention (especially in the context of thefollowing claims) are to be construed to cover both the singular and theplural, unless otherwise indicated herein or clearly contradicted bycontext. The terms “comprising,” “having,” “including,” and “containing”are to be construed as open-ended terms (i.e., meaning “including, butnot limited to,”) unless otherwise noted. Recitation of ranges of valuesherein are merely intended to serve as a shorthand method of referringindividually to each separate value falling within the range, unlessotherwise indicated herein, and each separate value is incorporated intothe specification as if it were individually recited herein. All methodsdescribed herein can be performed in any suitable order unless otherwiseindicated herein or otherwise clearly contradicted by context. The useof any and all examples, or exemplary language (e.g., “such as”)provided herein, is intended merely to better illuminate the inventionand does not pose a limitation on the scope of the invention unlessotherwise claimed. No language in the specification should be construedas indicating any non-claimed element as essential to the practice ofthe invention.

What is claimed is:
 1. An aerogel blanket comprising a fibrous structureand an aerogel material within the fibrous structure, the aerogelmaterial comprising: (i) smoke suppressing filler embedded within theaerogel material, and (ii) hydrophobic materials covalently attached tothe aerogel material.
 2. The aerogel material of claim 1 wherein saidfillers comprise: phosphates, borates, metal silicates, metallocenes,molybdates, stannates, hydroxides, carbonates, metal oxides, antimony,magnesium-zinc blends, magnesium-zinc-antimony blends, or a combinationthereof.
 3. The aerogel material of claim 2 wherein at least some of thefillers are in hydrated form.
 4. The aerogel material of claim 2 whereinthe phosphate fillers comprise cyclic phosphates, alkylphosphates,ammonium polyphosphates, arylphosphates, alkarylphosphates or acombination thereof.
 5. The aerogel material of claim 4 wherein saidphosphates comprise triethyl phosphate, tributyl phosphate, trihexylphosphate, tridecyl phosphate, tri(2-ethylhexyl) phosphate, trioctylphosphate, hexyldioctyl phosphate, and the like.
 6. The aerogel materialof claim 2 wherein the phosphate fillers are present at a level of about1 to 50 percent all by weight of the final composition.
 7. The aerogelmaterial of claim 2 wherein the borate fillers comprise Magnesium,Sodium, Calcium, Zinc, Tantalum, Nickel, Titanium, Cerium, Potassium,Beryllium, Lithium, Antimony, Aluminum, Manganese, Copper, Strontium,Iron, ammonia or a combination thereof.
 8. The aerogel composite ofclaim 2 wherein the borate fillers are present at a level of about 1 to50 percent all by weight of the final composition.
 9. The aerogelmaterial of claim 2 wherein the metal silicate fillers compriseBeryllium, Magnesium, Calcium, Strontium, Barium, Radium, Aluminum,Iron, Titanium, Manganese, Potassium, Sodium or a combination thereof.10. The aerogel material of claim 2 wherein the metal silicate fillersare present at a level of about 1 to 50 percent all by weight of thefinal composition.
 11. The aerogel material of claim 2 wherein themetallocene fillers comprise Chromium, Cobalt, Hafnium, Iron, Titanium,Vanadium, Ruthenium, Rhodium, Zirconium, Tungsten, Molybdenum, Osmium,or Nickel.
 12. The aerogel material of claim 2 wherein the metallocenefillers are present at a level of about 1 to 50 percent all by weight ofthe final composition.
 13. The aerogel material of claim 2 wherein themolybdate fillers comprise: MoS₂, MoO₃, CaMoO₄, Mo₂O₅, MoS₃, Mo₂S₃,Mo₂O₃, MoO₂, MoS₄, MoCl₃, MoBr₃, PbMoO₄, ammonium 5-molybdocobaltate(III), 9-molybdonickelate (IV), 6-molybdoaluminate (III),6-molybdochromate (III), ammonium dimolybdate, ammonium molybdate,ammonium heptamolybdate, ammonium octamolybdate, ammoniumphosphomolybdates, alkali metal molybdates, alkaline earth molybdates ora combination thereof.
 14. The aerogel material of claim 2 wherein themetal oxide filler comprises zinc oxides, aluminum oxides, titaniumoxides, iron titanium oxides, antimony oxides, iron oxides, magnesiumoxides, zirconium oxides, iron titanium oxides, and chromium oxides. 15.The aerogel material of claim 2 wherein the antimony filler comprisesantimony trioxide, antimony tetraoxide, antimony pentaoxide, antimonysilicooxide, antimony sulfide, antimony tribromide, and antimonytetrachloride
 16. The aerogel material of claim 1 wherein the fibrousstructure is in a woven, nonwoven, mat, felt, batting, or a combinedform.
 17. A method comprising: (a) forming a gel precursor mixturecomprising gel precursors and smoke suppressing fillers; b) dispensingthe gel precursor mixture into a fibrous structure; c) forming a gelfrom the gel precursor mixture; and d) drying the gel.
 18. The method ofclaim 17, wherein the method further comprises incorporating hydrophobicmaterials which are covalently attached to the gel material
 19. Themethod of claim 17 wherein the fillers comprise: phosphates, borates,metal silicates, metallocenes, molybdates, stannates, hydroxides,carbonates, metal oxides, antimony, magnesium-zinc blends,magnesium-zinc-antimony blends, or a combination thereof.
 20. The methodof claim 19 wherein at least some of the fillers are in hydrated form.21. The method of claim 17 wherein the gel precursor mixture is formedby mixing an amount of a smoke suppressing filler with an amount of gelprecursor in a suitable solvent.
 22. The method of claim 17 wherein thefibrous structure comprises a woven, nonwoven, mat, felt, batting, or acombined form.
 23. The method of claim 17 wherein the gel is dried witha supercritical fluid which comprises carbon dioxide.
 24. An aerogelcomposite comprising a flexible reinforcing structure, and an aerogelmaterial within the reinforcing structure, wherein the aerogel materialcomprises: (i) an embedded smoke suppressing filler, and (ii) covalentlyattached hydrophobic materials.
 25. The aerogel composite of claim 24wherein said fillers comprise: phosphates, borates, metal silicates,metallocenes, molybdates, stannates, hydroxides, carbonates, metaloxides, antimony, magnesium-zinc blends, magnesium-zinc-antimony blends,or a combination thereof.
 26. The aerogel composite of claim 25 whereinat least some of the fillers are in hydrated form.